1. Field of the Invention
This invention relates to novel mixtures, curable under the action of UV radiation, containing unsaturated polyester resins and to the use thereof for the production of coatings on any desired substrates, in particular on wood or imitation wood.
2. Description of the Prior Art
Unsaturated polyester resins have long been known as binders for UV-curing coatings. DE-AS 1,694,149, for example, discloses that mixtures of unsaturated polyesters and polymerizable monomers may be cured by UV radiation with the addition of certain benzoin compounds. Due to the inhibitory action of atmospheric oxygen, lacquer coatings based on this system are often inadequately cured on the surface.
The addition of paraffins (xe2x80x9cparaffin polyestersxe2x80x9d), which accumulate on the surface during gelation, to avoid air inhibition in the case of conventional curing with peroxides is possible only to a certain extent because the thermal energy emitted by the UV light sources prevents the formation of the protective paraffin film. In these cases, a prior so-called pregelling zone must be provided.
Unsaturated polyesters which contain xcex1,xcex2-unsaturated dicarboxylic acid residues and allyl ether and/or polyalkylene glycol residues (xe2x80x9cgloss polyestersxe2x80x9d) require no paraffin for curing the surface of the lacquer film because the ether groups initiate an autooxidative drying process. UV curing of such resins with allyl ether groups (DE-OS 2,113,998) or polyalkylene glycol residues (DE-OS 3,010,428) results, as does conventional curing, in readily sandable coatings, but the reactivity of such resins is often too low to ensure sufficiently high processing speeds.
EP-A 0,195,968 describes curable resin compositions based on one or more unsaturated polyesters which contain terminal dicyclopentenyl ester groups and are thus intended to exhibit extended storage stability. However, the claimed polyester resins are not suitable for curing under UV light.
EP-A- 0,284,888 describes unsaturated polyesters which, due to the incorporation of inter alia norbornene dicarboxylic acid residues, combine good levelling with rapid curing. However, this applies only at an application viscosity for curtain coating of greater than 60 seconds (DIN 4 cup, 23xc2x0 C.), which is achieved by dilution with styrene. Recently, however, there has been demand for binders which are equally rapidly curable at still greater dilution, i.e., at an application viscosity for curtain coating of less than 60 seconds, and in which the properties of the resulting coatings, such as hardness and scratch resistance, do not worsen. Lower viscosity is associated with advantages in deaeration and levelling of the lacquer films.
An object of the present invention is to provide unsaturated polyester resins which are suitable for the production of coating compositions which may be crosslinked under the action of UV radiation and cure rapidly with good levelling even when highly diluted with styrene and/or at a low application viscosity.
Surprisingly, this object may be achieved with the compositions according to the invention described hereinafter, which contain polyester resins as the primary component. Achieving the stated object is surprising because the desired more rapid curability even when highly diluted with styrene is not solely dependent upon the concentration of the olefinic double bonds incorporated in the polyester resins as would be expected, but may instead only be achieved if structural components a1) and a2) are simultaneously incorporated into the polyester resins in the quantities disclosed in greater detail below.
The present invention relates to compositions that may be cured under the action of UV radiation and contain
A) 40 to 80 parts by weight of a polyester resin component containing one or more ethylenically unsaturated polyester resins which have an acid value of 0 to 50 and a hydroxyl value of 10 to 150 and are the reaction product of
a) 35 to 50 mole % of a carboxylic acid component containing
a1) 5 to 35 mole % of a 1,2-alkenyl dicarboxylic acid monodicyclopentenyl ester,
a2) 50 to 95 mole % of fumaric acid, maleic acid and/or maleic anhydride and
a3) 0 to 20 mole % of a carboxylic acid and/or a carboxylic anhydride other than a1) and a2) with
b) 50 to 65 mole % of an alcohol component containing
b1) 75 to 100 mole % of a dihydric alcohol,
b2) 0 to 25 mole % of a monohydric alcohol and
b3) 0 to 10 mole % of a trihydric alcohol,
B) 20 to 60 parts by weight of a monomer component containing one or more copolymerizable monomers and
C) 0.1 to 10 parts by weight of an initiator component containing one or more photoinitiators, wherein the parts by weight of A) and B) and the percentages of a) and b) each add up to 100.
The present invention also relates to coated substrates, in particular wood or imitation wood, prepared from these compositions at an application viscosity of less than 60 seconds measured at 23xc2x0 C. in a DIN 4 cup to DIN 53211 under the action of UV radiation.
Polyester resins A) have an acid value of 0 to 50, preferably 5 to 40 mg KOH/g; a hydroxyl value of 10 to 150, preferably 10 to 130 mg KOH/g; and a number average molecular weight (Mn, which may be determined by vapor pressure osmometry) of 300 to 5000, preferably 500 to 2000.
The polyester resins according to the invention are produced using known methods, for example by melt or azeotropic esterification of alcohols and acids or the esterifiable derivatives thereof, c.f. Methoden der organischen Chemie (Houben-Weyl), 4th edition, volume 14/2, Georg Thieme Verlag, Stuttgart 1961, page 1 to 5, 21 to 33, 40 to 44.
The polyester resins are produced by reacting components a1) to a3) and b1) to b3) in the previously disclosed ratios. Component a) preferably contains 6 to 30 mole % of a1), 60 to 94 mole % of a2) and 0 to 15 mole % of a3). Component b) preferably contains 80 to 95 mole % of b1), 5 to 20 mole % of b2) and 0 to 5 mole % of b3). 1,2-alkenyl dicarboxylic acid monodicyclopentenyl ester a1) is the reaction product of maleic acid and dicyclopentadiene and is preferably produced in a preceding stage by heating a mixture of 1.0 mole of maleic anhydride, 1.0 mole of water and 1.0 mole of dicyclopentadiene at a temperature of 80 and 140xc2x0 C.
Once the remaining components have been added, esterification proceeds under an inert gas atmosphere at temperatures of 140 to 230xc2x0 C. For the esterification reaction the starting materials are preferably used in quantities corresponding to an OH/COOH equivalent ratio of 1:1 to 1.5:1, in which acid anhydride groups considered for purposes of this calculation as divalent groups.
Component a2) is selected from fumaric acid, maleic acid and/or maleic anhydride.
Component a3) is selected from saturated or unsaturated aliphatic dicarboxylic acids having 4 to 10 carbon atoms other than those set forth for component a2), such as succinic acid, adipic acid, sebacic acid, itaconic acid and/or anhydrides of such acids; cycloaliphatic dicarboxylic acids or dicarboxylic anhydrides having 8 to 10 carbon atoms, such as tetrahydrophthalic acid, hexahydrophthalic acid, norbornene dicarboxylic acid and their anhydrides; aromatic dicarboxylic acids having 8 carbon atoms or their anhydrides, such as phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid; and aliphatic, cycloaliphatic and/or aromatic monocarboxylic acids having 2 to 10 carbon atoms, such as benzoic acid, acetic acid, cyclohexane carboxylic acid and 2-ethyl-hexanoic acid.
Component b1) is selected from dihydric alcohols having 2 to 15 carbon atoms, such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol, dipropylene glycol, the isomeric butanediols, neopentyl glycol, 1,6-hexanediol, 2-ethylhexanediol and tripropylene glycol. Ethylene glycol, 1,2-propanediol, 1,3-propanediol, diethylene glycol and dipropylene glycol are preferred.
Component b2) is selected from monohydric alcohols having 1 to 12 carbon atoms, such as methanol, ethanol, n-hexanol, isooctanol, n-decanol, diethylene glycol monobutyl ether and benzyl alcohol.
Component b3) is selected from tri- to tetrahydric alcohols having 3 to 20 carbon atoms such as glycerol, trimethylolpropane, pentaerythritol and their alkoxylation products containing ether groups and up to 20 carbon atoms.
In order to protect the polyester resins from unwanted premature polymerization, it is often advisable to add during their production 0.001 to 0.1 wt. %, based on the weight of the starting materials used for the production of the polyesters, of known polymerization inhibitors or antioxidants, such as the quinones, hydroquinones, copper compounds, phosphites, amines or phenols conventionally used for this purpose.
Styrene is preferably used as all or a portion of component B) in the compositions according to the invention. However, other copolymerizable monomers, such as (meth)acrylic acid esters and monomers containing vinyl ether groups may also be used as component B) or as a proportion of component B).
Suitable photoinitiators C) are known and include those described, for example, in Methoden der organischen Chemie (Houben-Weyl), volume E 20, page 80 et seq., Georg Thieme Verlag, Stuttgart 1987. Examples include benzoin ethers such as benzoin isopropyl ether, benzil ketals such as benzil dimethyl ketal, and hydroxyalkyl phenones such as 1-phenyl-2-hydroxy-2-methylpropan-1-one and benzophenone and the derivatives thereof.
The photoinitiators are used in quantities of 0.1 to 10 wt. %, preferably 0.1 to 5 wt. %, based on the weight of the compositions according to the invention. Either one photoinitiator may be used or mixtures of different photoinitiators may be used to obtain advantageous synergistic effects.
The compositions according to the invention may optionally contain known additives D), which include inhibitors, metal compounds, carriers, extenders, thixotroping agents, levelling agents, and smoothing and flatting agents.
The compositions according to the invention are suitable for coating various substrates, such as paper, plastic films, paperboard and in particular wood or imitation wood. Application may be achieved using any methods conventional in lacquer technology such as curtain coating, spraying and rolling. The xe2x80x9cdelivery formxe2x80x9d of the compositions according to the invention frequently differs from the finally used xe2x80x9capplication formxe2x80x9d by the addition of a further quantity of component B), in particular styrene, to reduce the viscosity. Both the xe2x80x9cdelivery formxe2x80x9d and the xe2x80x9capplication formxe2x80x9d of the composition preferably fall within the previously disclosed ranges.
All percentages stated in the following examples are weight percentages, unless otherwise indicated.